Dyeing cellulose derivative materials



Patented Oct. 21, 1941 DYEING CELLULOSE DERIVATIVE MATERIALS Cyril M.Croft, George Seymour, and Walter Brooks, Cumberland, Md., assignors toCelanese Corporation of America, a corporation of Delaware No Drawing.Application April 22, 1939, Serial No. 269,414

6 Claims. (01. 8-59) This invention relates to improvements in thecoloration or dyeing of textile materials made of or containingcellulose acetate or other organic derivatives of cellulose.

An object of this invention is the dyeing of textile materialscontaining organic derivatives of cellulose such as cellulose acetate.

. will appear from the following detailed description and the claims.

It is well known that cellulose acetate and other cellulose ester andcellulose ether materials have no, or a very limited, affinity for largeclasses of dyes such'as acid colors used for dyeing wool. cottondyestuffs, vat dyes and alsocertain basic dyestuffs. The coloration ordyeing of cellulose acetate materials is therefore usually effected bymeans of water insoluble dyestuffs applied to the Another obJect of thisinvention is the dyeing of cellulose liquids which have a swellingaction on the cellulose acetate or other organic derivative ofcellulose. Best results are obtained when using a mixture of organicliquids which has a swelling effect on the cellulose derivative, theamount of mixture being from about to 10% on the weight material in theform of aqueous suspensions or procedure. It is obvious that any processwhich makes possible the use of new classes of dyestufi's for thecoloration of cellulose acetate is of the utmost importance. only makespossible the use oi these classes of dyes for dyeing cellulose acetatebut also improves the dyeings obtained with dyestuils which have a goodaflinity for the cellulose acetate.

a We have'found that if dyestuffs are applied to textile materials oforganic derivative of cellulose in the presenceof comparatively. smallamounts of certain swelling or softening agents for the organicderivative of cellulose, excellent dyeings or colorations can beobtained. I Thus dyestufis which normally have no afiinity for or effectupon organic derivative of cellulose materials will give dyeings ofexcellent shade and fastness when applied in accordance with thepresentfinvention. Where dyestuffs having an aflinityfor celluloseacetate are employed, it is possible, as a result of our invention, toobtaina greater depth oi" shade in a shorter space of time.

In accordance with our invention we dye materials containing celluloseacetate or other organic derivatives of cellulose by treating the samein a bath containing, in addition to a suitable The present inventionnot.

of the bath. The amount of swelling liquid will of course vary with thespecific liquid employed a in the mixture.

The textile material to be treated may be in the form of a fabriccontaining yarns of organic derivatives of cellulose such as organicesters of cellulose or cellulose ethers but it may also be in the formof yarns, or more particularly, staple fibers. Examples of organicesters of cellulose are cellulose acetate, cellulose formate, cellulosepropionate, cellulose butyrate or mixed esters such as cellulose acetatepropionate and cellulose acetate butyrate. Examples of cellulose ethersare methyl cellulose, ethyl cellulose and benzyl cellulose. may be madeentirely of the cellulose derivative or it may be a mixed materialcontaining, for example, cotton, natural silk, reconstituted celluloseor wool in addition'to the cellulose derivative. By proper selection of.the dyestuffs various novel effects can be obtained with such mixedtextile materials- As pointed outabove, the present invention ispredicated on the use of small amounts of a mixture of organic-liquidswhich have a swelling action on the cellulose derivative in the dyebath.

Examples of organic liquids which we have found and triethyl phosphate.The following also gave satisfactory results: dioxan, glycerol formal,

7 methyl acetate, ethyl acetate, butyl carbitol, carbitol acetate andcellosolve acetate. Excellent results were obtained by adding, for eachliter of dye,bat.h, a mixture comprising 30 cc. of glycerol butal, 30cc. of glycerol monochlorhydrln and 3 cc. of glacial acetic acid.

Various classes of dyestuffs may be used in carrying out the presentinvention. Thus direct cotton colors, acid wool colors and indigisolsmay be applied to cellulosederivative materials with highly satisfactoryresults even though these dyes have no afiinity for oreffect uponcellulose de-' rivative material when applied in the usual manner. Thepresent invention is also of value in connection with the waterinsoluble dyes which are normally appliedin the form of dispersions orsuspensions for the dyeing of cellulose derivadyestufl', comparativelysmall amounts of organic tives, for it'makes' possible theobtaining of aThe textile material treated Example I A dye bath was made up asfollows:

Parts Water 1130 Glycerol butal 30 Ethylene chlorhydrin j 30 Glacialacetic acid 3 W001 Fast Blue GL. 3. 5

Sodium chloride (added during the course of dyeing) 60. Sodium sulphate(added during the course of dyeing) 60 A fabric, approximately 100 partsby weight,

of cellulose acetate yarn was dyed in the above bath on a jig at 70 to'l5 0., giving a temperature of fabric on the roll of 55 to 65 C. Saltadditions were made after one-half hour's dyeing, the second half beingadded after another half hour's being dyeing. Thedyeing was continuedfor a total of two hours. The dye bath was kept level in the jig bymaking frequent additions of 1% ethylene chlorhydrin and water. The bathwas fairly exhausted after two hours and the fabric was dyed. a goodblue. If desired a small amount of Gardinol may be added to the bath tofix the dye more firmly in the fabric.

Other acid wool dyestuffs can be employed under similar conditions inplace of Wool Fast Blue GL.

I Example II A dye bath was prepared as follows:

Parts Water 1, 000 Glycerol butal 30 Glycerol monochlorhydrin' 30Glacial acetic acid 3 Celliton Fast Blue FR, 3

Approximately 100 parts by weight of cellulose acetate staple fiber weredyed in the above-mentioned bath at a temperature of 70 C. for 15'minutes. Sixty. parts of sodium chloride were added during the'course ofthe dyeing, and the dyeing was continued for a further 15 minutes at 70C. The ratio of liquid to material treated was in the proportion ofapproximately 10:1. The staple fiber was dyed a fine bright blue. Thematerial was dyed to a greater depth of shade in a shorter time than wassimilar material in an identical bath without the organic liquids.

Other dyestuffs of the SBA type that could be used to advantage are: SRABlue-i, SRA Scarlet 3, SRA Red 8 and SRA Rubine 9.

' Example III A bath was prepared as follows:

Parts Water 1, 000 Glycerol butal 30 Glycerol monochlorhydrin 30 Aceticacid 3 Gyco Neutral Blue CWR 3 .A cellulose acetate staple abewas dyed mthe above-mentioned bath for 15 minutes at 70 C. Sixty parts of sodiumchloride were added during the dyeing, and the dyeing was continued fora further 15 minutes at 70 C. "The cellulose acetate staple fiber 'usedin dyeing was approximately parts, giving the ratio of bath to theamount of material treated of 10:1. The staple fiber was dyed a finelight blue shade, although under normal conditions Gyco Neutral Blue CWRhas no affinity whatever for cellulose acetate.

Other acid dyestufis that could be used satisfactorily are: Azo 'Rubinol3GP, Alizarine Light Brown BL, Gyco Neutral Blue CWL, Gyco Neutral BlueR, Wool Fast Blue GL (Color Index Example IV A dyebath was prepared asfollows, all of the parts being by weight:

Parts Water 1, 000 Glycerol butal 30 Glycerol monochlorhydrin 30 Sodiumnitrite 10 Algosol Blue 043 3 Sodium chloride 60 Example V A dyebath wasprepared as follows:

Parts Water g 1,000 Glycerol butal 3o Glycerol monochlorhydrin. 30Acetic acid 3 Chrysophenine G, Color Index 365 3 100 parts of celluloseacetate staple fiber were dyed in the above-mentioned bath for 15minutes at 70 C. 60 parts of sodium chloride were added during thedyeing and the dyeing was continued for a further 15 minutes at 70 C.The cellulose acetate staple fiber was dyed a beautiful shade of yellowalthough Chrysophenine G normally has no afllnityfor cellulose acetate.

Other cotton dyestuiis which can also be used are Amanil Scarlet B andErie Catechine G.

The foregoing detailed description is given merely by way ofillustration and many variations may be made therein without departingfrom the spirit of our invention. 1

Having described our invention, what'we de-' sire to secure by LettersPatent is:

1. Method of dyeing material containing an organic derivative ofcellulose, which comprises treating said material in a bath containing adyestufi having substantially no aflinity for the organic, derivative oi-cellulose and which contains acid groups and 5 to 10%, ,on the weightof the bath, of a. mixture of glycerol butal,. glycerol monochlorhydrinand acetic acid in which mixture the glycerol butal and the glycerolmonochlorhydrin are present in equal proportions and togethervcompriseamajor portion of the mixture, and the acetic acid is present in smallamount. I

I cellulose staple fibers, which comprises treating 2. Method of.dyeingtextile material containing an organic derivative of cellulose, whichcomprises treating said material in a bath containing a dyestufl havingsubstantially no aflinity for the organic derivative of cellulose andwhich contains acid groups'and 30 cc. per liter of v glycerol butal,30cc. per liter of glycerol monochlorhydrin and3 cc. per literof aceticacid.

3. Method of dyeing organic derivative of said staple fibers in a. bathcontaining a dyestufi having substantially no afiinity for the organicderivative of cellulose and which contains acid groups and 30 cc. perliter of glycerol butal,'30 cc. per liter of glycerol monohlorhydrin and3 cc. per liter of acetic acid. I

x 4. Method of dyeing material containing cellulose acetate, whichcomprises treating said" material in a. bath containing a dyestuifhaving substantially no affinity for the cellulose acetate and whichcontains acid groups and 5 to 10%, on the weight of the bath, of a.mixture of glycerol butal, glycerol monochlorhydrin and acetic acid inwhich mixture the glycerol butal and the glycerol monochlorhydrin arepresent in equal proportions and together comprise a major portion ofthe mixture, and the acetic'acid is present in small amount.

5. Method of dyeing textile'material containing cellulose acetate, whichcomprises treating said materialin a bath containing a dyestufi havingsubstantially no aflinity for the cellulose acetate and which containsacid groups and cc. per'liter of glycerol butal, 30 cc. per liter ofglycerol monochlorhydrin and 3 cc. per liter of acetic acid.

6.Method of dyeing cellulose acetate staple fibers, which com'prisestreating said staple fibers in a bath containing a dyestuif havingsubstantially no affinity for the cellulose acetate and which containsacid groups and 30 cc. per liter of glycerol butal, 30 cc. per liter ofglycerol monochlorhydrin and '3 cc. per liter of acetic acid.

' CYRIL M. CROFT.

GEORGE W. SEYMOUR. WALTER BROOKS. I

